179694-35-0Relevant articles and documents
Structure-Guided Regulation in the Enantioselectivity of an Epoxide Hydrolase to Produce Enantiomeric Monosubstituted Epoxides and Vicinal Diols via Kinetic Resolution
Hou, Xiao-Dong,Hu, Bo-Chun,Hu, Die,Lei, Yu-Qing,Rao, Yi-Jian,Wu, Min-Chen,Zhang, Dong
supporting information, p. 1757 - 1761 (2022/03/16)
Structure-guided microtuning of an Aspergillus usamii epoxide hydrolase was executed. One mutant, A214C/A250I, displayed a 12.6-fold enhanced enantiomeric ratio (E = 202) toward rac-styrene oxide, achieving its nearly perfect kinetic resolution at 0.8 M in pure water or 1.6 M in n-hexanol/water. Several other beneficial mutants also displayed significantly improved E values, offering promising biocatalysts to access 19 structurally diverse chiral monosubstituted epoxides (97.1 - ≥ 99% ees) and vicinal diols (56.2-98.0% eep) with high yields.
Method for synthesizing chiral 1,2-diol compound
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Paragraph 0027; 0041-0044, (2021/07/21)
The invention relates to a method for synthesizing a chiral 1,2-diol compound, which comprises the following steps: sequentially adding a cobalt catalyst, a ligand, alpha-hydroxy ketone, an organic solvent and silane into a reaction system at 20-30 DEG C in a nitrogen atmosphere, then stirring the mixture, and carrying out column chromatography separation on the obtained product to obtain the chiral 1,2-diol compound. The high-yield cobalt catalyst in the earth crust is used, meanwhile, cheap silane (PMHS, 500 g/298 yuan) is used as a reducing agent, the asymmetric reduction reaction of alpha-hydroxy ketone can be efficiently achieved under the mild condition, and the chiral 1,2-diol compound with high yield and optical activity is obtained. Moreover, through the creative labor of the inventor, the reaction yield can reach 99%, and meanwhile, the content of the target product in the generated reaction product is 99% (namely, the yield is 99%, 99% ee).
Lewis Base Catalyzed Dioxygenation of Olefins with Hypervalent Iodine Reagents
Pan, Liangkun,Ke, Zhihai,Yeung, Ying-Yeung
supporting information, p. 8174 - 8178 (2021/10/25)
1,2-Diols are extremely useful building blocks in organic synthesis. Hypervalent iodine reagents are useful for the vicinal dihydroxylation of olefins to give 1,2-diols under metal-free conditions, but strongly acidic promoters are often required. Herein, we report a catalytic vicinal dioxygenation of olefins with hypervalent iodine reagents using Lewis bases as catalysts. The conditions are mild and compatible with various functional groups.
Catalytic Diastereo- and Enantioconvergent Synthesis of Vicinal Diamines from Diols through Borrowing Hydrogen
Feng, Wei,Gao, Taotao,Lau, Kai Kiat,Lin, Yamei,Pan, Hui-Jie,Yang, Binmiao,Zhao, Yu
supporting information, p. 18599 - 18604 (2021/08/09)
We present herein an unprecedented diastereoconvergent synthesis of vicinal diamines from diols through an economical, redox-neutral process. Under cooperative ruthenium and Lewis acid catalysis, readily available anilines and 1,2-diols (as a mixture of diastereomers) couple to forge two C?N bonds in an efficient and diastereoselective fashion. By identifying an effective chiral iridium/phosphoric acid co-catalyzed procedure, the first enantioconvergent double amination of racemic 1,2-diols has also been achieved, resulting in a practical access to highly valuable enantioenriched vicinal diamines.
Iodine-Initiated Dioxygenation of Aryl Alkenes Using tert-Butylhydroperoxides and Water: A Route to Vicinal Diols and Bisperoxides
Gao, Xiaofang,Lin, Jiani,Zhang, Li,Lou, Xinyao,Guo, Guanghui,Peng, Na,Xu, Huan,Liu, Yi
, p. 15469 - 15480 (2021/11/16)
An environment-friendly and efficient dioxygenation of aryl alkenes for the construction of vicinal diols has been developed in water with iodine as the catalyst and tert-butylhydroperoxides (TBHPs) as the oxidant. The protocol was efficient, sustainable, and operationally simple. Detailed mechanistic studies indicated that one of the hydroxyl groups is derived from water and the other one is derived from TBHP. Additionally, the bisperoxides could be obtained in good yields with iodine as the catalyst, Na2CO3 as the additive, and propylene carbonate as the solvent, instead.
Manipulating regioselectivity of an epoxide hydrolase for single enzymatic synthesis of (: R)-1,2-diols from racemic epoxides
Hu, Die,Zong, Xun-Cheng,Xue, Feng,Li, Chuang,Hu, Bo-Chun,Wu, Min-Chen
supporting information, p. 2799 - 2802 (2020/03/13)
Both the activity and regioselectivity of Phaseolus vulgaris epoxide hydrolase were remarkably improved via reshaping two substrate tunnels based on rational design. The elegant one-step enantioconvergent hydrolysis of seven rac-epoxides was achieved by single mutants, allowing green and efficient access to valuable (R)-1,2 diols with high eep (90.1-98.3%) and yields.
Reprogramming Epoxide Hydrolase to Improve Enantioconvergence in Hydrolysis of Styrene Oxide Scaffolds
Li, Fu-Long,Qiu, Yan-Yan,Zheng, Yu-Cong,Chen, Fei-Fei,Kong, Xu–Dong,Xu, Jian-He,Yu, Hui-Lei
, p. 4699 - 4706 (2020/09/21)
Enantioconvergent hydrolysis by epoxide hydrolase is a promising method for the synthesis of important vicinal diols. However, the poor regioselectivity of the naturally occurring enzymes results in low enantioconvergence in the enzymatic hydrolysis of styrene oxides. Herein, modulated residue No. 263 was redesigned based on structural information and a smart variant library was constructed by site-directed modification using an “optimized amino acid alphabet” to improve the regioselectivity of epoxide hydrolase from Vigna radiata (VrEH2). The regioselectivity coefficient (r) of variant M263Q for the R-isomer of meta-substituted styrene oxides was improved 40–63-fold, and variant M263V also exhibited higher regioselectivity towards the R-isomer of para-substituted styrene oxides compared with the wild type, which resulted in improved enantioconvergence in hydrolysis of styrene oxide scaffolds. Structural insight showed the crucial role of residue No. 263 in modulating the substrate binding conformation by altering the binding surroundings. Furthermore, increased differences in the attacking distance between nucleophilic residue Asp101 and the two carbon atoms of the epoxide ring provided evidence for improved regioselectivity. Several high-value vicinal diols were readily synthesized (>88% yield, 90%–98% ee) by enantioconvergent hydrolysis using the reprogrammed variants. These findings provide a successful strategy for enhancing the enantioconvergence of native epoxide hydrolases through key single-site mutation and more powerful enzyme tools for the enantioconvergent hydrolysis of styrene oxide scaffolds into single (R)-enantiomers of chiral vicinal diols. (Figure presented.).
Exploiting Designed Oxidase-Peroxygenase Mutual Benefit System for Asymmetric Cascade Reactions
Yu, Da,Wang, Jian-Bo,Reetz, Manfred T.
, (2019/04/17)
A unique P450 monooxygenase-peroxygenase mutual benefit system was designed as the core element in the construction of a biocatalytic cascade reaction sequence leading from 3-phenyl propionic acid to (R)-phenyl glycol. In this system, P450 monooxygenase (P450-BM3) and P450 peroxygenase (OleTJE) not only function as catalysts for the crucial initial reactions, they also ensure an internal in situ H2O2 recycle mechanism that avoids its accumulation and thus prevents possible toxic effects. By directed evolution of P450-BM3 as the catalyst in the enantioselective epoxidation of the styrene-intermediate, formed from 3-phenyl propionic acid, and the epoxide hydrolase ANEH for final hydrolytic ring opening, (R)-phenyl glycol and 9 derivatives thereof were synthesized from the respective carboxylic acids in one-pot processes with high enantioselectivity.
Exploiting Designed Oxidase-Peroxygenase Mutual Benefit System for Asymmetric Cascade Reactions
Yu, Da,Wang, Jian-Bo,Reetz, Manfred T.
, p. 5655 - 5658 (2019/04/17)
A unique P450 monooxygenase-peroxygenase mutual benefit system was designed as the core element in the construction of a biocatalytic cascade reaction sequence leading from 3-phenyl propionic acid to (R)-phenyl glycol. In this system, P450 monooxygenase (P450-BM3) and P450 peroxygenase (OleTJE) not only function as catalysts for the crucial initial reactions, they also ensure an internal in situ H2O2 recycle mechanism that avoids its accumulation and thus prevents possible toxic effects. By directed evolution of P450-BM3 as the catalyst in the enantioselective epoxidation of the styrene-intermediate, formed from 3-phenyl propionic acid, and the epoxide hydrolase ANEH for final hydrolytic ring opening, (R)-phenyl glycol and 9 derivatives thereof were synthesized from the respective carboxylic acids in one-pot processes with high enantioselectivity.
Bifunctional organocatalysts for the conversion of CO2, epoxides and aryl amines to 3-aryl-2-oxazolidinones
Xie, Ya-Fei,Guo, Cheng,Shi, Lei,Peng, Bang-Hua,Liu, Ning
supporting information, p. 3497 - 3506 (2019/04/14)
A route to synthesize 3-aryl-2-oxazolidinones is developed, which is achieved through a three component reaction between CO2, aryl amines, and epoxides with a binary organocatalytic system composed of organocatalysts and DBU (1,8-diazabicyclo[5.4.0]undec-7-ene). The method allows wide scopes of epoxide and aryl amine substrates with various functional groups under mild reaction conditions. The control experiments indicate that a cyclic carbonate is formed via cycloaddition of epoxides with CO2, which further reacts with the β-amino alcohol originating from epoxides and aryl amines, resulting in the formation of 3-aryl-2-oxazolidinones finally.
